CN105899600A - 全氟弹性体组合物、以及密封材料和其制造方法 - Google Patents
全氟弹性体组合物、以及密封材料和其制造方法 Download PDFInfo
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- CN105899600A CN105899600A CN201480070928.5A CN201480070928A CN105899600A CN 105899600 A CN105899600 A CN 105899600A CN 201480070928 A CN201480070928 A CN 201480070928A CN 105899600 A CN105899600 A CN 105899600A
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- Prior art keywords
- perfluoroelastomer
- cross
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- perfluoroelastomer composition
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- 229920006169 Perfluoroelastomer Polymers 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000003566 sealing material Substances 0.000 title abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 125000002560 nitrile group Chemical group 0.000 claims abstract description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008393 encapsulating agent Substances 0.000 claims description 33
- -1 alkyl vinyl ether Chemical compound 0.000 claims description 23
- 238000004132 cross linking Methods 0.000 claims description 18
- 239000011256 inorganic filler Substances 0.000 claims description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 14
- 238000000465 moulding Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000470 constituent Substances 0.000 abstract 3
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 14
- 230000006835 compression Effects 0.000 description 11
- 238000007906 compression Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000013329 compounding Methods 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229920001780 ECTFE Polymers 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229950000845 politef Drugs 0.000 description 3
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 3
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 2
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical class NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- KECOIASOKMSRFT-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(O)C(N)=CC(S(=O)(=O)C=2C=C(N)C(O)=CC=2)=C1 KECOIASOKMSRFT-UHFFFAOYSA-N 0.000 description 1
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NLNRQJQXCQVDQJ-UHFFFAOYSA-N bis(3,4-diaminophenyl)methanone Chemical compound C1=C(N)C(N)=CC=C1C(=O)C1=CC=C(N)C(N)=C1 NLNRQJQXCQVDQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1009—Fluorinated polymers, e.g. PTFE
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/02—Sealings between relatively-stationary surfaces
- F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
- F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/02—Sealings between relatively-stationary surfaces
- F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
- F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
- F16J15/102—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing characterised by material
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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- General Engineering & Computer Science (AREA)
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Abstract
提供全氟弹性体组合物、以及由该全氟弹性体组合物的交联物形成的密封材料和其制造方法,所述全氟弹性体组合物包含:全氟弹性体100重量份,其含有源自四氟乙烯的构成单元、源自全氟(烷基乙烯基醚)或全氟(烷氧基烷基乙烯基醚)的构成单元和源自含腈基全氟乙烯基醚的构成单元;氟树脂1重量份以上且小于25重量份;和,规定的交联剂。
Description
技术领域
本发明涉及全氟弹性体组合物、以及使用其的密封材料和其制造方法。
背景技术
作为各种用途中使用的密封材料(垫片、密封件等),已知有由氟橡胶形成的密封材料,构成半导体制造装置的等离子体蚀刻装置、等离子体CVD装置中,例如作为用于将对晶片进行处理的工艺腔室保持为真空的密封材料,氟橡胶中,使用了由耐热性和耐等离子体性(基于等离子体的耐分解性)特别优异的全氟弹性体形成的密封材料。另外,例如对于将半导体制造装置中的腔室和输送部分隔的闸部中使用的密封材料,为了重复压缩和开放,还要求合适的机械强度。
由氟橡胶形成的密封材料的机械强度可以通过配混无机填充剂来改善。然而,将配混有无机填充剂的密封材料用于上述那样的半导体制造装置用途时,即使使用耐等离子体性优异的全氟弹性体的情况下,在严格的等离子体环境下密封材料的全氟弹性体成分有时也被等离子体蚀刻,上述情况下,配混的无机填充剂在腔室内飞散,有导致腔室污染、半导体的制品不良的问题的担心。
日本专利第2937302号说明书(专利文献1)中记载了一种等离子体蚀刻装置的密封材料用组合物,其包含全氟弹性体和聚四氟乙烯树脂粉末,且硫化后的溶出金属量为规定值以下。
现有技术文献
专利文献
专利文献1:日本专利第2937302号说明书
发明内容
发明要解决的问题
本发明的目的在于,提供即使不配混可能导致上述那样问题的无机填充剂也可以形成维持良好的耐热性(压缩永久变形特性)、且机械强度(硬度、弹性模量)也优异的密封材料的全氟弹性体组合物、以及使用其的密封材料和其制造方法。
用于解决问题的方案
本发明提供以下所示的全氟弹性体组合物、以及密封材料和其制造方法。
[1]一种全氟弹性体组合物,其包含:
全氟弹性体100重量份,其含有源自四氟乙烯的构成单元、源自全氟(烷基乙烯基醚)或全氟(烷氧基烷基乙烯基醚)的构成单元和源自含腈基全氟乙烯基醚的构成单元;
氟树脂1重量份以上且小于25重量份;和,
交联剂,其选自由下述通式(1)所示的双(氨基苯酚)化合物、
下述通式(2)所示的双(氨基苯硫酚)化合物
和下述通式(3)所示的四胺化合物组成的组中的至少1种。
[式(1)~(3)中,A为SO2、O、C=O、碳数1~6的亚烷基、碳数1~10的全氟亚烷基或2个苯环直接连接的碳-碳键。式(1)和(2)中,位于同一苯环上的NH2基与OH基或SH基彼此相邻,并且NH2基和OH基或SH基相对于A基处于间位或对位。]
[2]根据[1]所述的全氟弹性体组合物,其中,前述交联剂的含量相对于前述全氟弹性体100重量份为0.05~5重量份。
[3]根据[1]或[2]所述的全氟弹性体组合物,其中,前述氟树脂的含量相对于前述全氟弹性体100重量份为3~20重量份。
[4]根据[1]~[3]中任一项所述的全氟弹性体组合物,其中,不含无机填充剂。
[5]一种密封材料,其是由[1]~[4]中任一项所述的全氟弹性体组合物的交联物形成的。
[6]根据[5]所述的密封材料,其用于半导体制造装置。
[7]一种密封材料的制造方法,其包括将[1]~[4]中任一项所述的全氟弹性体组合物进行交联成型的工序。
[8]根据[7]所述的制造方法,其中,前述进行交联成型的工序包括通过电离性辐射线使其交联的工序。
发明的效果
根据本发明,可以提供即使在不配混无机填充剂的情况下,交联后也具有良好的耐热性(压缩永久变形特性)且机械强度也优异的全氟弹性体组合物。不配混无机填充剂的情况下,可以抑制无机填充剂的飞散(颗粒的产生)所导致的腔室污染、半导体的制品不良。本发明的全氟弹性体组合物可以作为密封材料用、尤其半导体制造装置用途的密封材料用适合地应用。
具体实施方式
<全氟弹性体组合物>
〔a〕全氟弹性体
本发明中使用的全氟弹性体为含有源自四氟乙烯的构成单元I、源自全氟(烷基乙烯基醚)或全氟(烷氧基烷基乙烯基醚)的构成单元II和源自含腈基全氟乙烯基醚的构成单元III的三元共聚物。利用以该全氟弹性体为主要成分的全氟弹性体组合物,可以提供耐等离子体性优异的交联成型物(密封材料等)。
全氟(烷基乙烯基醚)的烷基的碳数可以为1~5,例如可以为:全氟(甲基乙烯基醚)、全氟(乙基乙烯基醚)、全氟(丙基乙烯基醚)等。优选为全氟(甲基乙烯基醚)。
全氟(烷氧基烷基乙烯基醚)的与乙烯基醚基(CF2=CFO-)键合的基团的碳数可以为3~11,例如可以为:
CF2=CFOCF2CF(CF3)OCnF2n+1、
CF2=CFO(CF2)3OCnF2n+1、
CF2=CFOCF2CF(CF3)O(CF2O)mCnF2n+1、或
CF2=CFO(CF2)2OCnF2n+1。
上述式中,n例如为1~5,m例如为1~3。
含腈基全氟乙烯基醚为交联部位单体,例如可以为:
CF2=CFO(CF2)nOCF(CF3)CN(n例如为2~4)、
CF2=CFO(CF2)nCN(n例如为2~12)、
CF2=CFO[CF2CF(CF3)O]m(CF2)nCN(n例如为2,m例如为1~5)、
CF2=CFO[CF2CF(CF3)O]m(CF2)nCN(n例如为1~4,m例如为1~2)、或
CF2=CFO[CF2CF(CF3)O]nCF2CF(CF3)CN(n例如为0~4)。
全氟弹性体中的各构成单元的比率即构成单元I/构成单元II/构成单元III之比以摩尔比计通常为50~74.8%/25~49.8%/0.2~5%,优选为60~74.8%/25~39.5%/0.5~2%。本发明的全氟弹性体组合物也可以包含构成单元I/构成单元II/构成单元III之比不同的2种以上的全氟弹性体。
全氟弹性体也可以使用市售品,其一例为Dyneon株式会社制造的商品名“PFE131TZ”。
〔b〕氟树脂
氟树脂为分子内具有氟原子的树脂,例如可以为:聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)、四氟乙烯-六氟丙烯共聚物(FEP)、四氟乙烯-乙烯共聚物(ETFE)、聚氯三氟乙烯(PCTFE)、氯三氟乙烯-乙烯共聚物(ECTFE)、聚偏二氟乙烯(PVDF)、聚氟乙烯(PVF)、偏二氟乙烯六氟丙烯共聚物(VDF-HFP共聚物)、偏二氟乙烯六氟丙烯-四氟乙烯共聚物(VDF-HFP-TFE共聚物)等。氟树脂可以仅单独使用1种,也可以组合使用2种以上。
上述中,高温下使用成型品时,从防止树脂熔融而破坏压缩永久变形等特性的观点出发,优选使用熔点高的PFA、PTFE。
氟树脂可以含有官能团。官能团例如可以通过使具有该官能团的单体共聚而导入。作为具有官能团的单体,使交联部位单体共聚时,在进一步提高全氟弹性体组合物的交联成型物的机械强度等的方面是有利的。交联部位单体与上述含腈基全氟乙烯基醚同样地可以为含腈基单体。作为含有官能团的氟树脂的例子,可以举出:日本特开2013-177631号公报所述的含腈基聚四氟乙烯。
另外,氟树脂例如也可以为“TFM改性PTFE”(Dyneon株式会社制造)那样的、经过改性的氟树脂。
全氟弹性体组合物中的氟树脂的含量(使用2种以上的氟树脂时为其总量)相对于全氟弹性体100重量份设为1重量份以上且小于25重量份,优选为3~24重量份,更优选为3~20重量份。设为1重量份以上时,在提高所得交联成型物(密封材料等)的机械强度的方面变得有利。另外,通过设为小于25重量份,可以兼顾良好的机械强度和良好的耐热性(压缩永久变形特性)。氟树脂的含量变为25重量份以上时,显示弹性的全氟弹性体的含量相对减少,压缩永久变形特性恶化。
需要说明的是,1重量份以上且小于25重量份这样的氟树脂含量为较少的含量,但根据本发明,通过基于后述规定交联剂的交联体系的应用,可以实现优异的机械强度。
〔c〕交联剂
本发明的全氟弹性体组合物包含选自由上述通式(1)所示的双(氨基苯酚)化合物、上述通式(2)所示的双(氨基苯硫酚)化合物和上述通式(3)所示的四胺化合物组成的组中的至少1种交联剂。利用基于该交联剂的交联体系,使以腈基作为交联部位的全氟弹性体交联,从而虽然氟树脂含量较少,但是可以对交联成型物赋予优异的机械强度。
氟树脂具有腈基那样的交联部位的情况下,通过上述交联剂氟树脂的交联也进行,可以有助于机械强度进一步提高。
优选使用的交联剂的具体例例如包含:2,2-双(3-氨基-4-羟基苯基)六氟丙烷(BOAP);4,4’-磺酰基双(2-氨基苯酚)〔双(3-氨基-4-羟基苯基)砜〕、3,3’-二氨基联苯胺、3,3’,4,4’-四氨基二苯甲酮。优选使用BOAP。
对于全氟弹性体组合物中的交联剂的含量(使用2种以上的交联剂时为其总量),优选为使全氟弹性体的交联部位(进而根据需要氟树脂所具有的交联部位)全部交联所需的充分量,典型地,相对于全氟弹性体100重量份,优选为0.05~5重量份,更优选为0.1~3重量份,进一步优选为0.1~1.5重量份。
全氟弹性体组合物可以含有除了上述通式(1)~(3)以外的其他交联剂或交联催化剂,例如可以包含:三嗪交联体系的交联催化剂即锡化合物、磷化合物、氮化合物。其中,其他交联剂或交联催化剂的含量从交联成型物的机械强度的观点出发,相对于上述通式(1)~(3)的交联剂100重量%,优选为50重量%以下,更优选为20重量%以下,进一步优选为10重量%以下,特别优选为0重量%。
〔d〕其他配混剂
本发明的全氟弹性体组合物以改善加工性、调整物性等为目的,可以根据需要包含防老剂、抗氧化剂、硫化促进剂、加工助剂(硬脂酸等)、稳定剂、增粘剂、硅烷偶联剂、增塑剂、阻燃剂、脱模剂、蜡类、润滑剂等添加剂。添加剂可以仅使用1种也可以组合使用2种以上。
但是,将密封材料用于半导体制造装置用途时,由于挥发、溶出或析出而有产生制造工序污染、半导体制造効率降低的担心,从而优选添加剂的量尽量少(例如,相对于全氟弹性体100重量份为10重量份以下,优选为5重量份以下,更优选为2重量份以下,进一步优选为1重量份以下),期望不含有添加剂。
另外,本发明的全氟弹性体组合物也可以根据需要包含:炭黑、二氧化硅、氧化铝、氧化锌、氧化钛、粘土、滑石、硅藻土、硫酸钡、碳酸钙、碳酸镁、氧化钙、云母、石墨、氢氧化铝、硅酸铝、水滑石、金属粉、玻璃粉、陶瓷粉那样的填充剂。
但是,填充剂中,特别是无机填充剂如上述那样成为颗粒的原因,因此,将密封材料用于半导体制造装置用途时,无机填充剂的量优选尽量少(例如,相对于全氟弹性体100重量份为10重量份以下,优选为5重量份以下,更优选为2重量份以下,进一步优选为1重量份以下),期望不配混无机填充剂。需要说明的是,无机填充剂是指,含有金属元素(Ba、Ti、Zn、Al、Mg、Ca、Si等)的填充剂。
〔e〕全氟弹性体组合物的制备
本发明的全氟弹性体组合物可以通过将全氟弹性体、氟树脂、交联剂和根据需要添加的其他配混剂均匀地混炼来制备。作为混炼机,例如可以使用开炼机那样的混炼机;捏合机、班伯里密炼机那样的混合机等以往公知的混炼机。这些配混剂可以一次性混合并混炼,或者也可以如将一部分配混剂混炼后、将剩余的配混剂混炼那样分成多阶段来将全部配混剂进行混炼。
如果提及全氟弹性体与氟树脂的混炼,则例如可以使用:1)使用混炼机将全氟弹性体粉末和氟树脂粉末进行混炼的方法;2)使用混合机将全氟弹性体粉末或粒料和氟树脂粉末或粒料进行熔融混炼的方法;以及,3)在全氟弹性体的制备阶段添加氟树脂的方法。
作为上述3)的方法,可以举出如下方法:将均由乳液聚合法得到的全氟弹性体的水性分散液和氟树脂的水性分散液混合,然后通过共凝固得到全氟弹性体和氟树脂的混合物。
<密封材料>
通过将上述全氟弹性体组合物进行交联成型(硫化成型),从而可以得到密封材料那样的交联成型物。交联成型可以根据需要将全氟弹性体组合物进行预成型后、使用模具进行压制成型来进行。成型温度例如为150~220℃左右。也可以通过送进压制成型、注射成型、挤出成型等进行成型。也可以根据需要,在150~280℃左右的温度下进行二次交联。
全氟弹性体组合物例如包含ETFE、PVDF、PCTFE、ECTFE、偏二氟乙烯六氟丙烯共聚物(VDF-HFP共聚物)、偏二氟乙烯-六氟丙烯-四氟乙烯共聚物(VDF-HFP-TFE共聚物)那样熔点较低的氟树脂的情况下,为了可以使用其熔点以上的密封材料,优选在进行上述那样的交联成型(压制成型等)后设置进一步照射电离性辐射线使其交联的工序。由此,可以维持能够耐于实用的程度的密封材料的压缩永久变形特性。作为电离性辐射线,可以优选使用电子束、γ射线。
密封材料可以为密封件、垫片等。密封材料的形状可以根据其用途而适当选择,其代表例是截面形状为O型的O环。本发明的密封材料不含有无机填充剂且可以具有良好的耐热性(压缩永久变形特性)和机械强度,因此特别适合作为半导体制造装置用途的密封材料使用。
实施例
以下,列举实施例和比较例更详细地说明本发明,但本发明不限定于此。
<实施例1~6、比较例1~9>
按照如下步骤,制备全氟弹性体组合物,接着制作密封材料。首先,按照表1所示的配方组成(表1中的配混量的单位为重量份),通过开炼机将各配混剂的规定量进行混炼。接着,将所得全氟弹性体组合物在180℃、25分钟(比较例3~8为170℃、20分钟)的条件下进行压制成型,然后在280℃、6小时(比较例3~5、7~8为300℃、5小时,比较例6为200℃、4小时)的条件下进行2次交联得到密封材料(O环)。
[表1]
实施例和比较例中使用的各配混剂的详细情况如下所述。
〔1〕FFKM1:四氟乙烯/全氟(烷基乙烯基醚)/含腈基全氟(烷基乙烯基醚)共聚物即含腈基全氟弹性体〔Dyneon株式会社制造的“PFE-131TZ”〕。
〔2〕FFKM2:全氟弹性体和氟树脂的混合物〔Dyneon株式会社制造的“PFE-133TBZ”〕。全氟弹性体为四氟乙烯/全氟(烷基乙烯基醚)/含腈基全氟(烷基乙烯基醚)共聚物即含腈基全氟弹性体。表1中,“FFKM2”的栏中示出FFKM2中所含的全氟弹性体的含量(重量份),“氟树脂1”的栏中示出FFKM2中所含的氟树脂的含量(重量份)。
〔3〕FFKM3:Solvay Specialty Polymers K.K.制造的“PFR94”。
〔4〕氟树脂2:聚四氟乙烯的微粉〔Dyneon株式会社制造的“TF9207Z”。
〔5〕BOAP:2,2-双(3-氨基-4-羟基苯基)六氟丙烷〔东京化成工业株式会社制造的“2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane(CAS编号:83558-87-6)”〕。
〔6〕三嗪交联体系催化剂:Dyneon株式会社制造的“PFE300C”。
〔7〕TAIC:三烯丙基异氰脲酸酯〔日本化成株式会社制造的“TAIC”〕。
〔8〕Perhexa 25B:2,5-二甲基-2,5-二(过氧化叔丁基)己烷〔日油株式会社制造的“Perhexa 25B”〕。
(密封材料的评价)
对于所得交联成型品(密封材料),测定下述项目并评价。将结果示于表1。
〔a〕密封材料的常态物性
依据JIS K6250,由制作成2mm厚度的片依据JIS K6251脱模为哑铃状3号型试验片。将该试验片以500mm/分钟进行拉伸,测定拉伸强度、断裂伸长率、100%弹性模量。另外,依据JIS K6253,利用A型硬度计硬度试验机测定片的硬度。这些试验均在25℃的温度下进行。
〔b〕密封材料的压缩永久变形
依据JIS K6262,在260℃×72小时、压缩率25%的条件下,使用线径O环测定压缩永久变形。
Claims (8)
1.一种全氟弹性体组合物,其包含:
全氟弹性体100重量份,其含有源自四氟乙烯的构成单元、源自全氟(烷基乙烯基醚)或全氟(烷氧基烷基乙烯基醚)的构成单元和源自含腈基全氟乙烯基醚的构成单元;
氟树脂1重量份以上且小于25重量份;和,
交联剂,其选自由下述通式(1)所示的双(氨基苯酚)化合物、下述通式(2)所示的双(氨基苯硫酚)化合物和下述通式(3)所示的四胺化合物组成的组中的至少1种,
式(1)~(3)中,A为SO2、O、C=O、碳数1~6的亚烷基、碳数1~10的全氟亚烷基或2个苯环直接连接的碳-碳键,式(1)和(2)中,位于同一苯环上的NH2基与OH基或SH基彼此相邻,并且NH2基和OH基或SH基相对于A基处于间位或对位。
2.根据权利要求1所述的全氟弹性体组合物,其中,所述交联剂的含量相对于所述全氟弹性体100重量份为0.05~5重量份。
3.根据权利要求1所述的全氟弹性体组合物,其中,所述氟树脂的含量相对于所述全氟弹性体100重量份为3~20重量份。
4.根据权利要求1所述的全氟弹性体组合物,其中,不含无机填充剂。
5.一种密封材料,其是由权利要求1所述的全氟弹性体组合物的交联物形成的。
6.根据权利要求5所述的密封材料,其用于半导体制造装置。
7.一种密封材料的制造方法,其包括将权利要求1所述的全氟弹性体组合物进行交联成型的工序。
8.根据权利要求7所述的制造方法,其中,所述进行交联成型的工序包括通过电离性辐射线使其交联的工序。
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JP2013271345A JP6230415B2 (ja) | 2013-12-27 | 2013-12-27 | パーフルオロエラストマー組成物、並びにシール材及びその製造方法 |
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PCT/JP2014/080026 WO2015098337A1 (ja) | 2013-12-27 | 2014-11-13 | パーフルオロエラストマー組成物、並びにシール材及びその製造方法 |
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CN113166478A (zh) * | 2018-12-04 | 2021-07-23 | 株式会社华尔卡 | 弹性体组合物以及密封件 |
CN114555728A (zh) * | 2019-08-12 | 2022-05-27 | 科慕埃弗西有限公司 | 粘附性无定形全氟聚合物组合物 |
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JP6990579B2 (ja) * | 2017-12-25 | 2022-01-12 | 三井・ケマーズ フロロプロダクツ株式会社 | 溶融成形用材料及びその製造方法 |
EP3766106B1 (en) * | 2018-03-15 | 2022-01-05 | Solvay Specialty Polymers Italy S.p.A. | Fluoropolymer composition for components of light emitting apparatus |
JP2023113432A (ja) * | 2022-02-03 | 2023-08-16 | 株式会社バルカー | 環状積層体、シール材および製造方法 |
WO2023189547A1 (ja) * | 2022-03-31 | 2023-10-05 | ダイキン工業株式会社 | 組成物、架橋物およびシール材 |
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CN105899600B (zh) | 2019-02-22 |
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KR20160104620A (ko) | 2016-09-05 |
JP2015124346A (ja) | 2015-07-06 |
WO2015098337A1 (ja) | 2015-07-02 |
SG11201605257UA (en) | 2016-08-30 |
EP3088460A1 (en) | 2016-11-02 |
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US20160319102A1 (en) | 2016-11-03 |
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